A precursor diblock copolymer with a silicon backbone, polystyrene-block-poly(methylvinylsiloxane), was synthesized, and 1H,1H,2H,2H-perfluorodecanethiol was quantitatively introduced into the backbone via a thiol-ene reaction to yield a novel coil-rod diblock copolymer, poly(styrene-block-poly(2-((3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)thio)ethyl)methylsiloxane). The ultra-hydrophobicity of the introduced perfluoroalkyl side chain enhanced the segregation between counter-blocks and significantly increased the χ value, which is essential for minimizing the size of self-assembled domains for lithographic applications. Thus, self-assembled domains with a minimal spacing of approximately 10 nm were formed. A hexagonally packed array with significant anisotropy was observed in the self-assembled morphology by small-angle X-ray scattering and transmission electron microscopy. Such an array was precisely reproduced by modified self-consistent field theory (SCFT) calculation developed for the coil-rod structure. Furthermore, the phase diagram was estimated, and the morphological dependence on the relative scale of the rod unit was investigated by SCFT prediction.
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